Effect of Nitrogen Atom Introduction on the Photocatalytic Hydrogen Evolution Activity of Covalent Triazine Frameworks: Experimental and Theoretical Study

Abstract The construction of high‐performance photocatalyst has always been explored. Covalent organic frameworks (COFs), especially keto‐amine‐linked COFs, have many advantages, such as adjustable bandgaps, π–π stacking structure, excellent response ability to visible light, high specific surface area, high mobility of carrier carriers, good physical and chemical stability, and so on, showing strong potential applications in photocatalytic solar energy conversion and hydrogen production. Two analogous covalent triazine frameworks (CTFs), T3H‐CTF and T3N‐CTF, have been synthesized via Schiff‐base condensation reactions between 2,4,6‐trihydroxybenzene‐1,3,5‐tricarbalehyde (MOP) and the corresponding triazine‐based aromatic amines under solvothermal condition. For T3N‐CTF, the peripheral aromatic linker to the central triazine unit was the pyridine unit, instead of the benzene unit in the T3H‐CTF unit. T3N‐CTF had a hydrogen production rate (HPR) of 6485.05 μmol g−1 h−1, much higher than that of T3H‐CTF (2028.06 μmol g−1 h−1). Accordingly, T3N‐CTF had a much higher apparent quantum yield (AQY) of 12.2 % than that of T3H‐CTF (4.12 %) at 405 nm. The experimental and theoretical results showed that the extended light absorption range, enlarged surface area, and enhanced separation and transportation efficiencies of charge carriers of T3N‐CTF compared with T3H‐CTF were uniformly induced by the introduction of peripheral nitrogen atoms into the skeleton of former CTF, which eventually boosted the visible‐light induced hydrogen evolution reaction (HER). The work suggests a new method for enhancing the intrinsic HER activity by modulating the electronic features of the conjugated COFs by the introduction of pyridinic N atoms.